METALLIC SOAPS FROM L I N S E E D OIL H =I
.
German .
Rubidium 84.75 Ruthenium ..roo.9 Samarium -149.2 ? 43.8 Scandium Selenium 78.6 Silicon 28.2 Silver ..IO7.11 Sodium 22.88 Strontium 86.95 Sulphur 31.83 Tantalum .IS1.5 Tellurium .126.1 Terbium .158.8 Thallium . 2 0 2.61 Thorium .230.8 ? Thulium 169.4 Tin 1 18.1 Titanium 47.8 Tungsten .IS 2.6 Uranium .237.8 Vanadium ........ 5 I .o Xenon .127. Ytterbium 171.9 Yttrium 88.3 Zinc 64.9 Zirconium 89.7
84-76 100.9 148.9 43.8 78.5
..... ........
........
.........
............ ...........
.......... .........
.......... ........ ........
......... ......... ......... .......... ............. ......... ........ ......... ........... ........ ........... .............. ........
21.5
.
0 = 16
Clarke.
.........
.
28.2
107.12
22.88 86.94 31.8; 181.6 I 26.
....
Clarke
.
85.4 101.7 150.3 ? 44.1 79.2 28.4 107.92 23.05 87.60 32.07 182.8 127.7 I60
.
German .
85.44 101.7 I50 . 44 . 79.2 28.4 107.93 23.05 87.68 32.065 183 127.5 ?
85.4 101.7 150. 44.1 79.1 28.4 107.93 23.05 87.6 32.06 183.
204 . I 232.5 171.
128. I73 89. 65.4 90.7
Richards
. 1 6 0.
.
202.6 230.8 170. 117.6 47.7 182.6 237.7 50.8
232.6 ? 170.7 119.0 48. I 5 184 239.6 51.4
204.15 233. 171 ? 119.0 48.17 184 238.5' 51.4
127
128.0
128
.
204.15
.
.
.
172 . 88.3 64.9
173.2 89.0 65.4
90.0
90.4
. I73.
89.0 65.40 90.6
127.
....
118.5 48.I 184. 239.5 512
.
.
METALLIC SOAPS FROM LINSEED OIL AN INVESTIQATION OF THEIR SOLUBILITIES IN CERTAIN OF THE HYDROCARBONS B Y HERMANN T. VULTE AND HARRIETWINFIELD GIBSON . Received October 19. 1901. N the analysis of mixed paints. two of the most important points to be determined are the nature and the amount of the drying agent contained therein. since upon the quality of the drier present the value of the paint is largely conditioned In modern practice. the driers used are almost invariably either the manganese or the lead soaps of linseed oil (so-called linoleates) or they are the resinates of the same metals. or they may be any mixture of these salts. T h e investigation of paint driers. therefore. resolves itself into a determination of the four salts mentioned . T h e method ordinarily pursued has been to separate the
.
1
.
1
From unpublished determinations by Richards and Merigold .
216
H E R N A K S T. YCLTE A N D H A R R I E T M'IKFIELD GIBSON.
base and the drier from the pigment by nieaiis of petroleum ether, the ethereal solution being then transferred to a tightly corked Erlenmeyer flask, and allowed to stand for from twelve to twenty-four hours. A somewhat gunimy sediment, white to yellow in color and more or less adherent to the sides of tlie flask, is deposited. The sediment is then separated from the ethereal solution, and carefully washed b y decantation with a further qiiantity of tlie petroleum ether. As, upon analysis, this sediment may be shown to consist mainly of the lead soap of linseed oil, together with some manganese soap, it has been assumed that a coniplete separation of the drier took place at this point and it was. therefore, believed that this method could be used in determining tlie character and amount of the drier. 17pon further trial this niethod has proved far from satisfactory aiid various hydrocarbons, ranging from petroleum ether to benzine, have been suggested as a substitute for the solvent employed. S o n e of these substitutes has been found to effect a perfect separation of the drier, although a distinct difference in solvent action has been observed. For example, the lead salts precipitate most quickly from petroleum ether aiid least from benzine. while the nianganese salts are, in comparison, but slightly affected by either, except on long standing. Since, then, a perfect separation of the drier from the base cannot be effected by any known solvent, it has been thought advisable to study the behavior of various metallic salts of linseed oil with different hydrocarbon solvents, and to determine the percentages of solubility a t the end of stated and uniforni periods. T h e work has been extended to cover the linseed oil soaps of most of the coninion metals, and the results of the inr.estigatioti are given in the following paper. The sodiuni soap of linseed oil was first prepared, great care being taken to effect complete saponification. The soap was curded out by excess lye, the use of salt being avoided. I t was then washed free of impurities as far as possible, framed and allowed to stand until perfectly hard and dry. T h e soap thus formed was light brown in color, and had a pronounced odor of linseed. With water it formed a golden yellow solution and afforded an abundant lather. A table follows, giving the petroleum solvents used, together with their boiling-points and specific gravities :
M E T A L L I C SOAPS FROM L I N S E E D OIL. Boiling-poin t.
...................... 3s0-55O ................................5 ~ O - 7 5 ~ .............................. 75O-85O .............................. 59O ............................. 62O .............................. 71° ............................. 74O
Petroleum ether.. Benzine Benzine.. Naphtha. Naphtha.. Benzine.. Gasolene.. Turpentine
...............................
217 Sp. gr. at 15' C.
0.639 0.702
0.695 0.741 0.732 0.698 0.699 0.855
I n the pr.eparation of the various metallic soaps whose solubility it was desired to test, a water solution of the sodium soap was first carefully cooled to 20' C. or below. This is essential, as many of the metallic soaps examlned have a very low melting-point. A soluble salt of the metal in question, exhibiting its lower valency if possible, was then selected, and a solution of this salt slowly added to the soap solution until precipitation ceased. The metallic soap was then washed by decantation with distilled air-free water, carefully dried, an excess amount added to each solvent, and the solutions allowed to stand in the dark. At the expiration of one hour, twenty-four hours, and forty-eight hours, I O cc. of the clear solution were carefully evaporated in a tared watch-glass over a water-bath and the gain in weight recorded as dissolved matter. From this, the actual percentages of solubility were calculated and the results obtained, together with any peculiarities of the different salts, will be found in the annexed tables. It was thought well to first classify the metals into groups according to the ordinary method pursued for qualitative analysis, and then to give a resume of the properties developed by each salt. For purposes of comparison, their solubility in turpentine, under the same conditions, is also given in these tables: T A B L E S G I V I N G THE AMOUNT O F DISSOLVED M A T T E R I N THE VARIOUS SOLVENTS.
GROUPONE. Lend. 35O-55O. 55O-75O.
gms. 0.0385 p.Ct. 0.602 gms. 0.0381 24 hrs. p. ct. 0.598 grns. 0.0376 48 hrs. p. Ct. 0.590 I
hr.
0.0276 0.393 0.0277 0.394 0.0277 0.394
75O-85O.
0.0477 0.686 0.0479 0.689 0.0471 0.678
59O.
0.0309 0.417 0.0318 0.428 0.0328 0.443
62O.
0.0276 0.377 0.0278 0.379 0.0273 0.373
7P.
0.0296 0.424 0.0286 0.409 0.0277 0.398
74O.
Turps.
0.0405 0.579 0.0413 0.591 0.0420
0.2494 2.917 0.2490 2.912
0.601
2.935
0.2510
218
HERMANN T. VULT$ AND H A R R I E T WINFIELD GIBSON.
GROUPTwo.
iVercu vy . 3j0-jj0.
gms. I hr. p. Ct. gms. 24hrs. p. ct. 48hrs. grns. p. ct.
550-75’3.
0.0138 0.0057 0.216 0.081 0.0376 0.0475 0.588 0.677 0.0500 0.0782 0.782 1.114
jjO-Sjo.
j90.
62O.
0.008s 0.0041 0.0067 0.122 0.055 0.091 0.0356 0.0155 0.0359 0.490 0.512 0.209 0.0672 0.0552 0.0435 0.967 0.735 0.594
71..
740.
0.0027 0.0093 0.039 0.133 0.0147 0.0542 0.211 0.776 0.0384 0.0899 0.550 1.286
Turps.
0.1692 1.979 0.2544 2.975 0.4593 5.372
Copper. 3j0-jj0,
gms. p. ct. gms. 24hrs. p. ct. 48hrs. gms. p. Ct. I hr.
jjo-750.
0.0285 0.0257 0.449 0.336 0.2516 0.3652 3.962 5.202 0,2534 0.4173 3.992 5.944
j90,
7j0-8j0.
0.0145 0.209 0.0962 1.384 0.0977 1.406
62O.
710.
74O.
0.0087 0.0124 0.1135 0.0609 0.117 0.169 1.626 0.871 0.1151 0.1094 0.1213 0.1032 1.553 1,494 1.738 1.476 0.1822 0.11720.1414 0.1886 2.459 1.601 2.026 2.698
Turps.
0.1238 1.448 0.4847 5.669 0.6625 7.748
GROUPTHREE. Tiii, 74c. Turps. 62@. 590, ire. g m s . 0.0435 0.0776 0.0926 0.0600 0.0804 0.0928 0.1216 0.2401 35O-jjo,
I
hr.
p,Ct. grns. 24hrs . p. ct. grns. 48hrs. p.ct.
jj0-7jo.
;j0-8jo.
0.681
1.105 1.332 0.0780 0.0921 0.801 1.111 1.325 0.0601 0.0787 0.0922 0.940 1 . 1 2 1 1.326
0.0520
0.809 0.0626 0.844 0.0661 0.S92
1.098 1.329 1.739 2.808 0.0867 0.0935 0.1322 0.2408 1.184 1.339 1.891 2.816 0.0885 0,0933 0.1389 0.2352 1.209 1.336 1.987 2.751
il?itintorLy, 35”-jj0.
gms. I hr. p. ct. grns. 24hrs. p.ct. grns. 48hrs. p. ct.
jjO-;jo.7jO-85
.
j9-.
0.0766 0.0877 0.0897 0.0703 1.198 1,249 1.291 0.948 0.1051 0.0965 0.0974 0.0702 1.631 1.374 1.401 0.947 0.1306 0.1155 0.1041 0.0742 2.043 1.645 1.498 1.001
62”.
ii
.
74’.
0.1069 0.0785 0.0608 1.462 1.124 0.869 0.1088 0.0814 0.0698 1.486 1.166 0.998 0.1104 0.0903 0.0746 1.508 1.294 1.067
Turps.
0.3496 4.088 0.3446 4.023 0.3432 4.014
GROUPFOUR.
(yon 3j3-5j0.
jjc-75”,
gms. 0.1887 0.2570 p , c t . 2.953 3.661 24hrs. gms. 0.3105 0.2g85 p. ct. 4.859 4.252 I
hr.
48hrs.
g m s . 0.2484 0.2251
p. ct. 3.887
3.206
753-8jc.
0.2589 3.725 0.3139 4.516 0.2483 3.572
j9’,
0.2878 3.884 0.3287 4.436 0.2895 3.907
623.
0.2635 3.599 0.2840 3.878 0.2130 2.gog
71’.
0.2087 2.989 0.1999 2.864 o.r53j 2.93
74’.
Turps.
0.6103 7.138 0.6424 7.513 0.1511 0.6424 2.161 7.513 0.1873 2.679 0.1837 2.711
METALLIC SOAPS FROM L I N S E E D OIL.
219
Chromium. 3 ~ O - 5 5 ~ .55O-750.
0.0455 p.Ct. 0,712 24hrs. gms. 0.0473 p. Ct. 0.740 gms. 0.0520 48 hrs. p. ct. 0.814 a hr.
gmS.
75O-85O.
0.0539 0.768 0.0646 0.920 0.0459 0.654
0.0645 0.928 0.0598 0.860 0.0501 0.721
59-750.
75O-85O.
59O.
62O.
0.0579 0.837 0.791 0.0902 0.0729 1.217 0.992 0.0571 0.0551 0.772 0.753 0.0620
7P.
74O.
Turps.
0.0595 0.852 0.0579 0.829 0.0497
0.0592 0.847 0.0597 0.854 0.0485 0.694
0.2293
0.712
2.682
0.3822 4.470 0.3853 4.506
Aluminum. 35O-55O.
z hr.
24hrs.
gmS.
p.ct. gms.
p. ct. gms. 48hrs. p.Ct.
0.0045 0.0033 0.047 0.070 0.0422 p.0610 0.660 0.868 0.0940 0.1038 1.471 1.479
0.0025 0.036 0.0439 0.632 0.0763 1.097
59O.
6 2 ' .
0.0097 0.029 0.132 0.019g 0.0378 0.268 0.516 0.0457 0.0570 0.617 0.779 0.0022
7io.
74?
0.0067 0.0036 0.096 0.052 0.0514 0.0351 0.736 0.502 0.0718 0.0509 1.029 0.728
Turps.
0.1796 2.101 0.1898 2.219
0.1941 2.270
GROUPFIVE.
Nickel. 35'35'.
55'-75'.
59'.
75-45'.
62'.
71'.
74".
Turps.
gms. 0.1094 0.1255 0.1282 0.0785 0.0851 0.1048 0.1127 0.2306 I hr. p. ct. 1.709 1.788 1.545 1.059 1.162 1.501 1.612 2.697
0.1584 0.1046 24hrs. g m s . 0.1933 0.1751 0.1874 p. ct. 3.025 2.494 2.696 2.138 1.429 gms. 0.1856 0.1703 0.1807 0.1583 0.0559 48hrs. 2.136 0.763 p. ct. 2.904 2,425 Z.&XJ
0.1277 0.1487 0,3769 1.829 2.127 4.408 0.0632 0.0873 0.3345 o.goc 1.249 3.912
Cobalt. 35'35'.
gms. p. ct. gms. 24hrs. p. ct. gms. 48hrs. p. ct. I
hr.
55'-75'.
75"-85'. O.OZOI
0.0172 0.0185 0.269 0.263 0.289 0.0204 0.0195 0.02og 0.319 0.278 0.301 0.0262 0.0181 0.0210 0.410 0.257 0.302
59'.
0.0143 0.193 0.0265 0.358 0.0343 0.463
62*.
71".
0.0176 0.0140 0.243 0.200 0.0270 0.0250 0.369 0.358 0.0386 0.0390 0.527 0.558
74".
Turps.
0.0082 0.3742 0.116 4.376 0.0157 0.2997 0.225 3.505 0.0271 0.3611 0.388 4.223
Manganese. 75'45'. 35-35', 55'-75'. 0.2280 0.0998 0.0896
59'.
0.0721 0.973 0.0899 1.213 gms. 0.0480 0.0276 0.0461 0.0282 48 hrs. p. ct. 0.751 0.393 0.663 0.381 gms. p. ct. 3.568 1.421 1.289 o.oggo 0.0840 24 hrs. gms. 0.2425 p.ct. 3.795 1.410 1.208
I
hr.
62'.
71'.
0.0673 0.964 0.0854 1.223 0.0281 0.0288 0.384 0.414
0.0702 0.959 0.0816 1.115
74'.
0.1077 1.541 o.og45 1.352 0.0403 0.576
Turps.
0.1827 2.137 o.iq8
2.454 0.2749 3.215
220
H E R M A N N T. VULTE A N D H A R R I E T W I N F I E L D GIBSON.
WUC.
gms. p.Ct. gms. 24 hrs. p. Ct. gms. 48 hrs. p. ct. I
hr.
35'-55'.
55'-75'.
0.0254 0.397 0.0536 0.838 0.0606 0.948
0.0492 0.0420 0.701 0.604 0.0792 0.0865 1.128 1.245 0.0715 0.0903 1.018 1.299
jj'-85'.
59'.
62'.
0.0310 0.418 0.0674 0.909 0.0649 0.876
0.0187 0.255 0.0640 0.874 0.0663 0.905
jl'.
74'.
Turps.
0.0424 0.0360 0.1870 0.607 0.515 2.187 0.0719 0.0706 0.2530 1.031 1.010 2.959 0.0846 0.0853 0.2946 1.212 1.220 3.445
GROUP SIX.
Bariuvt.' 35'35'.
gnis. p. ct. gms. 24 hrs. p. C t . I
hr.
0.0066 0.103 0.0062 0.097
55'-75'.
ije-sjo.
o.oom o.oorg 0.031 0.021 0.0040 0.0013 0.057 0.019
59'.
62'.
0.0072 0.042 o.og8 0.0024 0.0143 0.032 0.195 0.0031
7x0,
74'.
Turps-
0.0017 0.0007 0 . 1 2 2 8 0.024 0.001 1.436 0.0031 0.0027 0 . 1 3 0 ~ 0.044 0.039 1.522
Calcium .' 35'-55'.
5j'-75'.
7j'-85".
jg".
gms. 0.0154 0.0051 0.0053 0.0011 p , c t . 0.241 0.072 0.076 0.015 gms. 0 . 0 1 ~ 0 0.0064 0.0049 o.omg 24 hrs. p.ct. 0.188 0.091 0.070 0.012
I
hr.
62'.
71'.
74'.
Turps.
0.0109 0.0133 0.0045 0.1022 0.149 0.191 0.064 1.195 0.0098 0.0127 0.0042 0.1274 0.134 0.182 0.064 1.490
CONCLUSION.
A comparison of the figures given in the foregoing tables discloses the fact that certain of these metallic soaps, namely, those made of lead, nickel, iron and manganese, show marked individuality, the characteristics of each not being repeated by any other soap. I , The lead soap goes almost completely out of solution from all the petroleum solvents in less than one hour. 2. The nickel soap, while eventually affording a nearly complete separation, remains in solution for several days. 3. The iron soap, while giving a permanent solution of steadily increasing weight (due to oxidation), is an excellent drier on the application of slight heat. 4. T h e manganese soap is unique in its drying properties. As thus far conducted, the foregoing investigation discloses the following facts : I. The percentage of separation of the metallic soaps of linseed oil from their solutions in the hydrocarbon solvents is vari1 The percentage of dissolved matter was so small in the cases of barium and calcium that the investigation wa5 dropped at the expiration of twenty-four hours.
METALLIC SOAPS FROM LINSEED OIL.
c,
c
U U Y
9 9 G
" (n
& (n 0
i?
U
221
u Y
u
C. W. VOLNEY
222
able, differing with the nature of the solveiit and the character of the linoleate. 2. Each metallic soap affords a maximum percentage of solubility in some special hydrocarbon and, therefore, no one hydrocarbon solvent can be commended for all metals. 3. The time at which the maximum separation takes place is also variable, differing with the metal employed. It is, therefore, evident that a knowledge of the behavior of each soap with the different solvents is essential to the general analysis of driers and it is with the hope of contributing to t h i s knowledge that the present paper is submitted.
ON THE DECOilPOSlTlON OF SODIUM NITRATE BY S U L PHURIC ACID. PART Ill. RY
c. w
V0LsI:Y
Keccired 'Jvvciiilier
ii.
xgoi
ROM results of previously reported work, the author concluded' that the action of sulphuric acid on sodium nitrate takes place in two distinct phases, expressed by : 2NaN0, NaH,2S04
+ 2H,SO, = NaNO, + NaH,2S04 + "0,. .. . I + NaNO, = 2NaHS0, + HNO, .. . . . . . .. . . . .I1
and that these two phases of the process are marked by distinctly different temperatures. To obtain direct evidence for these conclusions, I have extended the experimental part of the investigation by producing in the retorts for distillation the exact condition for each phase, by using the materials, as represented therein. For the first phase, 85 grams of dry sodium nitrate with 2 0 0 grams of concentrated sulphuric acid were subjected to distillation, according to I. T h e distillation was carried out in the manner and apparatus already described, which gave observations for the temperatures of applied heat, the retort contents and distilling acid. In the following are given the results of this distillation, a s they were observed : 1
This Journal, 23,490
